Controlled chemoselective defluorination and non-defluorination for [5 + 1] aromatic annulation via Meisenheimer-type nitrogen anion and radical intermediates

Reported is a unique chemoselectivity approach to base-promoted defluorinative and Cu(i)-catalyzed aerobic oxidative non-defluorinative [5 + 1] condensation aromatizations of simple unsaturated ketones with ammonium salts via Meisenheimer-type nitrogen anion and radical intermediates. The CuBr/O(2) catalysis provides a straightforward approach to diverse 3-fluoropyridines in high yields. The synthetic utility of the strategy is highlighted by the concise synthesis of several F-modified bioactive compounds.